EP0879898B1 - Alliage de magnésium avec de bonnes propriétés à haute coulabilité - Google Patents

Alliage de magnésium avec de bonnes propriétés à haute coulabilité Download PDF

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Publication number
EP0879898B1
EP0879898B1 EP98106517A EP98106517A EP0879898B1 EP 0879898 B1 EP0879898 B1 EP 0879898B1 EP 98106517 A EP98106517 A EP 98106517A EP 98106517 A EP98106517 A EP 98106517A EP 0879898 B1 EP0879898 B1 EP 0879898B1
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alloy
magnesium based
magnesium
based alloy
alloys
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EP0879898A1 (fr
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Aihua A. Dr. Luo
Toru Shinoda
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Aisin Takaoka Co Ltd
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Aisin Takaoka Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting

Definitions

  • This invention relates to a magnesium based alloy.
  • the invention relates to a magnesium alloy having superior mechanical properties at elevated temperatures.
  • the alloy of this invention has excellent castability, and is particularly useful in die casting applications.
  • magnesium approximately 2/3 that of aluminum and 1/4 that of steel, makes it particularly attractive for transportation applications where weight reduction is critical.
  • Magnesium is also surprisingly strong for a light metal; in fact, it has the best strength-to-weight ratio of any commonly available cast metal,
  • magnesium can offer many other advantages such as good damping capacity, superior castability, excellent machinability, and good corrosion resistance.
  • the use of magnesium alloy parts in automobiles has experienced a rapid growth in recent years due to the ever-increasing demand of vehicle weight reduction.
  • Magnesium alloy parts can be fabricated by the conventional casting processes including die casting, sand casting, plaster casting, permanent mold casting and investment casting.
  • magnesium-aluminum based alloys for instance AM50A and AM60B alloys ("AM” designates aluminum and manganese additions) containing about S to 6 wt.% of aluminum and a trace amount of manganese; and magnesium-aluminum-zinc based alloys, for instance AZ91D (“AZ" designates aluminum and zinc additions) containing about 9 wt.% of aluminum and about 1 wt.% of zinc, are economically priced and widely used in the fabrication of automobile parts.
  • AM50A and AM60B alloys (“AM” designates aluminum and manganese additions) containing about S to 6 wt.% of aluminum and a trace amount of manganese
  • magnesium-aluminum-zinc based alloys for instance AZ91D (“AZ" designates aluminum and zinc additions) containing about 9 wt.% of aluminum and about 1 wt.% of zinc.
  • AZ91D designates aluminum and zinc additions
  • AE42 Another magnesium alloy which does provide some improved creep resistance is designated AE42 ("AE" designates aluminum and rare earth metal additions).
  • This alloy comprises about 4 wt. % of aluminum and about 2 wt.% of rare earth elements.
  • this alloy is difficult to die cast and uneconomical for volume production of automobile components.
  • the first group of alloys contain exotic and expensive elements such as silver, yttrium, rare earth, and zirconium, and they are primarily developed for gravity sand casting and use in aerospace and nuclear reactors.
  • the second group consists of a number of experimental alloys as disclosed in U.S. Patent Nos. 4,997,622; 5,078,962; and 5,147,603. These alloys were developed for rapid solidification processes such as melt-spinning or spray deposition in which the extremely high solidification rates (10 4 to 10 7 K/sec.) can be achieved.
  • a third publication entitled “Magnesium in the Volkswagen” by F. Hollrigl-Rosta. E. Just, J. Kohler and H.-J. Melzer (Light Metal Age, 22-29, August 1980), discloses that outstanding improvement of creep resistance was provided by addition of about 1 wt. % calcium to a magnesium alloy AZ81 which contains about 8 wt. % of aluminum and about 1 wt.% of zinc.
  • this publication discloses that the application of this alloy to the die casting production of crankcases (automotive parts) was not possible, because the castings stuck in the die and hot cracks occurred.
  • the present invention has been developed in order to solve the aforementioned problems of magnesium alloys. It is therefore a primary object of the present invention to provide a magnesium alloy with superior creep-resistance and tensile strength at elevated temperatures up to 150°C (better than or equal to those of AE42 alloy). It is a further object of the present invention to provide a magnesium alloy with improved tensile strength at room temperature (better than or equal to that of AZ91D alloy). It is yet another object of the present invention to provide a magnesium alloy which can be used to fabricate automotive components, which enables mass production by die casting, and which is available at low costs.
  • the present invention provides a magnesium alloy according to claim 1.
  • the alloy has superior creep and tensile properties at a temperature of up to 150°C, good castability and low costs.
  • the amount of aluminum varies from about 3 to about 7 wt. %.
  • the amount of zinc present in the alloy preferably varies from about 6 to about 10 wt. %.
  • the preferable range of calcium content in the alloy is from about 0.4 to about 1.5 wt.%.
  • the main constituent elements of the alloy are magnesium, aluminum, zinc and calcium.
  • the alloy may also contain other elements, such as from about 0.1 to about 0.5 wt. % of manganese, and up to about 0.05 wt. % of silicon; and impurities, such as less than about 0.004 wt. % of iron, less than about 0.001 wt.% of nickel, and less than about 0.008 wt.% of copper.
  • the alloy comprises from about 5 to about 30 volume % of the precipitates, more preferably from about 15 to about 25 volume %.
  • the alloy according to this invention may have a creep extension of less than about 0.6% at tensile stress of about 35 MPa and a temperature of about 150°C, as measured by ASTM Specification E139-95, and a yield strength of at least about 110 MPa at a temperature of about 150°C, as measured by ASTM Specification E21-92.
  • the alloy is particularly useful as a die casting alloy due to its high zinc content which results in improved castability (decreased hot-cracking and die-sticking).
  • the alloy of this invention also has good corrosion resistance (as measured by ASTM Specification B117-95) and is available at low costs.
  • the invention provides a die castable magnesium based alloy having improved properties at elevated temperatures yet enables economical and reproducible mass production of die cast parts using readily available and low cost alloy ingredients.
  • the alloy includes additions in amounts which achieve improved creep strength and die castability.
  • the alloy of this invention preferably comprises zinc, aluminum and calcium in a magnesium base alloy.
  • the compositional ranges of such additions in the present magnesium alloy provide the following advantages.
  • Aluminum is a well-known alloying element in magnesium based alloys as it contributes to the room-temperature strength and castability of the alloys. In order to obtain these advantageous effects, a minimum of 2 wt.%, and preferably at least 4 wt.% of aluminum should be included in the alloy according to the present invention. However, it is also known that aluminum has adverse effects on the creep resistance and tensile strength of magnesium alloys at elevated temperatures. This is because aluminum tends to, when its content is high, combine with the magnesium to form significant amounts of the intermetallic compound Mg 17 Al 12 , which has a low melting point (437°C) and therefore is deleterious to the high-temperature properties of magnesium based alloys. Accordingly, a preferred upper limit of the aluminum range is set at 9% by weight. A more preferred upper limit of aluminum is 7% by weight to achieve improvement in elevated temperature properties such as creep resistance and tensile strength.
  • calcium is the most economical (in comparison with silver, yttrium and various rare earth elements). It is therefore necessary to include calcium in an amount of 0.2% by weight or more.
  • the castability of the alloy is severely deteriorated to the extent that the alloy is no longer castable by the conventional die casting process.
  • a suitable amount zinc such as from about 6 to about 12 wt.%, more preferably from about 6 to about 10 wt.%.
  • calcium can be added in amounts up to 2 wt.%, preferably up to 1.5 wt.%, in order for the alloy to achieve the maximum creep resistance while maintaining good die-castability.
  • Zinc improves the room-temperature strength and castability of magnesium alloys, and up to 1 wt.% of zinc is commonly included in magnesium casting alloys such as the AZ91D.
  • a considerably higher zinc range i.e., from about 6 to about 12 wt.%, more preferably, about 6 to about 10 wt. %, is chosen based on two reasons: Firstly, as the aluminum content in the alloy is relatively low in order to achieve good high-temperature strength and creep resistance, high zinc contents are used as a supplement to enhance the room-temperature strength and castability of the alloy. Secondly, and more importantly, zinc surprisingly and unexpectedly restores the die-castability of magnesium alloys containing up to about 2 wt.% of calcium.
  • the upper limit of the zinc range is set at about 12 wt.%, more preferably, about 10 wt. % so that the density of the alloy remains low.
  • Die-sticking tendency of the alloys was rated 0 to 5 ("0" representing “no die-sticking” and "5" representing “most die-sticking") during the casting test using a steel die with no coating or spray, based on the ease of casting ejection, die cleaning and surface quality of the specimens.
  • Figure 2 shows the effect of calcium additions on the hot-cracking tendency of magnesium-aluminum based alloys (Mg-5%Al) containing two levels of zinc. It is evident that, when zinc is low; for example, at about 1 wt.%, the total crack length of the alloy increases dramatically with calcium contents up to about 1 wt.%, and then gradually decreases. However, when zinc is high, for instance, at about 8 wt. %, the effect of calcium on the total crack length of the alloy is minimal up to 2 wt. % of calcium addition.
  • the magnesium alloy in accordance with the present invention may also include lesser amounts of other additives and impurities. For example, from about 0.2 to about 0.5 wt. % of manganese can be added to the alloy to improve corrosion resistance. Silicon is a typical impurity element contained in the commercially pure magnesium ingots which are used to prepare magnesium alloys.
  • the alloy of this invention may contain up to 0.05 wt.% of silicon which has no harmful effects on the properties.
  • the alloy preferably contains less than about 0.004 wt.% of iron, less than about 0.001 wt.% of nickel, and less than about 0.008 wt.% of copper.
  • Mg-Al-Zn-Ca intermetallic phase results in the precipitation of a Mg-Al-Zn-Ca intermetallic phase.
  • This phase is generally positioned along the grain boundaries of the primary magnesium crystals in the alloy, as shown in Figure 4.
  • Figure 5 is the EDS (energy dispersive spectroscopy) analysis results for the intermetallic phase, which clearly shows that the compound contains aluminum, magnesium, zinc and calcium.
  • the magnesium based alloy of this invention has good creep resistance and high tensile strength at temperatures up to about 150°C.
  • the alloy preferably has a 200-hour creep extension of less than about 0.6% at 35 MPa and 150°C, more preferably less than about 0.3% under such test conditions.
  • the yield strength of the alloy at about 150°C is preferably higher than about 110 MPa, more preferably higher than about 115 MPa.
  • the alloy of the invention preferably has an ultimate tensile strength greater than 150 MPa, more preferably greater than 160 MPa. It is understood that the excellent high-temperature creep and tensile properties of the alloy result from the strengthening effect of the Mg-Al-Zn-Ca intermetallic phase in the alloy.
  • the alloy according to this invention contains from about 5 to about 30 volume % of the intermetallic phase, more preferably from about 15 to about 25 volume %.
  • the alloy according to this invention has good yield and tensile strengths at room temperature, as measured by ASTM Specification E8-96. At ambient temperature, the alloy preferably has a yield strength of at least about 145 MPa and an ultimate tensile strength of at least about 200 MPa, more preferably not less than about 150 MPa for the yield strength and not less than 210 MPa for the ultimate tensile strength.
  • the 200-hour salt spray corrosion rate of the alloy of this invention is preferably less than about 0.25 mg/cm 2 /day, more preferably less than about 0.16 mg/cm 2 /day.
  • the alloy of this invention has very good castability as evaluated by hot-cracking and die-sticking tendencies during casting.
  • the alloy is particularly tailored as a die casting alloy for mass production of automotive powertrain components.
  • the alloy may also be used to fabricate components by any other standard casting processes including gravity and pressure casting such as die casting in a hot or cold chamber die casting machine.
  • components can be fabricated from the alloy by other techniques including powder metallurgical and semi-solid processing techniques.
  • the production of the alloy of this invention can be performed by any standard alloy production process using standard melting and alloying equipment for magnesium.
  • the alloy according to this invention preferably does not contain any expensive ingredients so as to be economical for commercial production.
  • Magnesium based alloys having the following chemical compositions as set in Table 1 (wherein the balance of each alloy is Mg and unavoidable impurities) below were prepared using an electric resistance melting technique.
  • the alloys, designated as ZAC8502, ZAC8506 and ZAC8512, respectively, were melted and cast into test specimens using a 200-ton hot-chamber die casting machine at a casting temperature of 650°C. At least 200 sets of specimens, i.e., 200 shots of die cast parts, were made for testing and evaluation.
  • the resulting test specimens were subjected to creep testing at 150°C and 35 MPa (tensile stress) for 200 hours, and tensile testing at room temperature and 150°C. Creep testing was performed according to ASTM Specification E139-95, and the total creep extension was measured at 200 hours.
  • the creep test results in comparison with other magnesium based alloys, namely AZ91D and AE42, are illustrated in Figure 6.
  • Figure 6 shows that the creep extension of the alloys prepared according to the present invention, i.e., ZAC8502, ZAC8506 and ZAC8512, is approximately one order of magnitude less than that of standard magnesium based alloy AZ91D.
  • the alloys of this invention have a creep extension comparable to, or better than (in the case of ZAC8506 and ZAC8512) that of AE42 alloy at 150°C.
  • Table 2 summarizes the tensile test results for these alloys at 150°C measured by ASTM Specification E21-92.
  • TENSILE PROPERTIES AT 150°C Alloy ZAC8502 ZAC8506 ZAC8512 AZ91D AE42 0.2% yield strength (MPa) 120 117 118 110 107 ultimate tensile strength (MPa) 175 159 149 159 160 elongation (%) 115 10.5 5.1 6.7 36
  • the alloys of this invention have equivalent or slightly better yield strength, ultimate tensile strength and elongation at room temperature when compared with magnesium alloy AZ91D.
  • Table 3 further shows that the yield strength and ultimate tensile strength of the alloys according to the invention compare favorably with those of magnesium alloy AE42.
  • the ductility (elongation) of the alloy is lower than that of the AE42 alloy.
  • the alloys of this invention were also tested for salt spray corrosion performance according to ASTM Specification B117-95.
  • the 200-hour corrosion rates for the alloys in comparison with those of AZ91D and AE42 alloys are shown in Figure 7.
  • the alloys of this invention have similar corrosion resistance as other magnesium based alloys AZ91D and AE42.
  • the die-castability of the alloys was evaluated on a comparison basis. Each of the 200 die casting shots for each alloy was inspected for die-sticking and hot-cracking, and an overall rating of 0 to 5 ("0" representing "worst” and "5" representing "perfect") was given to each shot.
  • Figure 8 summarizes the average die-castability ratings for the alloys tested. The results suggest that the die-castability rating for the alloys of this invention is slightly lower than that of the AZ91D alloy (which is generally regarded as the "most die-castable" magnesium alloy) but significantly higher than that of the AE42 alloy.

Claims (20)

  1. Alliage à base de magnésium ayant des propriétés améliorées à hautes températures et une coulabilité améliorée, l'alliage comprenant, en % en poids, 2 à 9 % d'Al, 6 à 12 % de Zn, 0,1 à 2 % de Ca, éventuellement 0,1 à 0,5 % de Mn, jusqu'à 0,05 % de Si, le reste étant constitué de Mg et des impuretés inévitables telles que Fe, Ni, Cu.
  2. Alliage à base de magnésium selon la revendication 1, dans lequel l'alliage comprend 3 à 7 % d'Al, 6 à 10 % de Zn et 0,4 à 1,5 % de Ca.
  3. Alliage à base de magnésium selon la revendication 1, qui comprend 0,2 à 0,5 % de Mn.
  4. Alliage à base de magnésium selon la revendication 1, qui comprend jusqu'à 0,004 % de Fe.
  5. Alliage à base de magnésium selon la revendication 1, qui comprend jusqu'à 0,001 % de Ni.
  6. Alliage à base de magnésium selon la revendication 1, qui comprend jusqu'à 0,008 % de Cu.
  7. Alliage à base de magnésium selon la revendication 1, dans lequel l'alliage comprend des précipités d'un composé intermétallique Mg-Al-Zn-Ca.
  8. Alliage à base de magnésium selon la revendication 7, dans lequel l'alliage comprend d'environ 5 à environ 30 % en volume des précipités.
  9. Alliage à base de magnésium selon la revendication 7, dans lequel l'alliage comprend d'environ 15 à environ 25 % en volume des précipités.
  10. Alliage à base de magnésium selon la revendication 1, dans lequel l'alliage est essentiellement exempt de Si.
  11. Alliage à base de magnésium selon la revendication 1, dans lequel l'alliage, après coulée, présente des propriétés à hautes températures, à 150°C, correspondant à une limite élastique d'au moins 110 MPa et un allongement au fluage inférieur à environ 0,6 % après 200 heures à 150°C et sous une contrainte de traction d'environ 35 MPa.
  12. Alliage à base de magnésium selon la revendication 1, dans lequel l'alliage comprend une pièce coulée sous pression.
  13. Alliage à base de magnésium selon la revendication 1, dans lequel l'alliage est presque exempt de particules de Mg17Al12.
  14. Alliage à base de magnésium selon la revendication 1, dans lequel l'alliage comprend une quantité de Ca suffisante pour augmenter la résistance mécanique à hautes températures et la résistance au fluage, l'alliage contenant une quantité de Zn suffisante pour compenser la dégradation de la coulabilité sous pression due à la présence de Ca.
  15. Alliage à base de magnésium selon la revendication 1, coulé sous pression pour donner une pièce façonnée à l'aide d'une machine de coulée sous pression.
  16. Alliage à base de magnésium selon la revendication 1, qui est constitué de 3 à 6 % d'Al, de 7 à 10 % de Zn, de 0,1 à 0,4 % de Ca, éventuellement de 0,1 à 0,5 % de Mn, le reste étant constitué de Mg et des impuretés inévitables.
  17. Alliage à base de magnésium selon la revendication 1, qui est constitué de 3 à 6 % d'Al, de 7 à 10 % de Zn, de 0,4 à 0,8 % de Ca, éventuellement de 0,1 à 0,5 % de Mn, le reste étant constitué de Mg et des impuretés inévitables.
  18. Alliage à base de magnésium selon la revendication 1, dans lequel l'alliage est pour ainsi dire exempt de métaux des terres rares.
  19. Alliage à base de magnésium coulé selon la revendication 1, ayant des propriétés améliorées à hautes températures, l'alliage comprenant Al, Zn, Ca et Mg, l'alliage contenant des précipités de MgwAlxZnyCaz, où w = 20 à 40 % en atomes, x = 15 à 25 % en atomes, y = 15 à 30 % en atomes et z = 2 à 20 % en atomes.
  20. Alliage à base de magnésium selon la revendication 19, dans lequel l'alliage contient de 5 à 30 % en volume des précipités.
EP98106517A 1997-05-21 1998-04-08 Alliage de magnésium avec de bonnes propriétés à haute coulabilité Expired - Lifetime EP0879898B1 (fr)

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US861056 1997-05-21
US08/861,056 US5855697A (en) 1997-05-21 1997-05-21 Magnesium alloy having superior elevated-temperature properties and die castability

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EP0879898B1 true EP0879898B1 (fr) 2001-07-18

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US (1) US5855697A (fr)
EP (1) EP0879898B1 (fr)
JP (1) JP3354098B2 (fr)
CN (1) CN1088762C (fr)
AU (1) AU730893B2 (fr)
CA (1) CA2238070C (fr)
DE (1) DE69801133T2 (fr)

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CN103849798B (zh) * 2012-11-30 2017-11-07 沈阳工业大学 一种高强度铸造镁合金及其制备方法
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AU730893B2 (en) 2001-03-15
EP0879898A1 (fr) 1998-11-25
JP3354098B2 (ja) 2002-12-09
CA2238070A1 (fr) 1998-11-21
US5855697A (en) 1999-01-05
CN1210897A (zh) 1999-03-17
JPH10324941A (ja) 1998-12-08
CN1088762C (zh) 2002-08-07
DE69801133T2 (de) 2001-12-06
DE69801133D1 (de) 2001-08-23
AU6711398A (en) 1998-11-26
CA2238070C (fr) 2004-03-16

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